Sample Excitation Apparatus and Method for Spectroscopic Analysis

ABSTRACT

Sample excitation apparatus for a spectrometric analyser, the apparatus comprising a sample introduction stage comprising an electrospray nebuliser for generating a nebulised sample; and a sample excitation stage arranged to operate in an atmospheric pressure environment and to receive and excite the nebulised sample in a sample excitation region for spectrometric analysis thereof. ‘Excitation’ includes ionisation in ICP and MIP, flame excitation in AES, and optical excitation in AAS. For example, analyte solution ( 38 ) is fed out of the outlet end of a capillary ( 30,40,60,96 ), to a plasma source. A potential difference is applied between the capillary, its outlet end or the analyte solution and an opposing effective (counter) electrode, which may comprise a tube ( 64 ), a grid ( 80 ), or the plasma ( 34 ) itself, to promote formation of smaller droplets ( 46 ). The pressure of the plasma source is similar to the pressure in the region of the capillary outlet end.

FIELD OF THE INVENTION

This invention relates to a sample excitation apparatus and method forsupplying and exciting a sample in a plasma generator, a flame, oranother sample excitation device for subsequent spectroscopic analysisof the sample. In particular, the invention finds application in thefollowing elemental analysis techniques, among others: inductivelycoupled plasma mass spectrometry (ICP-MS), microwave induced plasma massspectrometry (MIP-MS), plasma optical (or atomic) emission spectroscopy(ICP/MIP-OES/AES, in particular using the iCAP ICP spectrometermanufactured by Thermo Fisher Scientific Inc.), atomic emissionspectroscopy

(AES) and atomic absorption spectroscopy (AAS). In all of the abovetechniques, the sample ionisation/excitation device is arranged tooperate in an atmospheric pressure environment.

BACKGROUND OF THE INVENTION

Sample introduction apparatuses in the form of nebulisers for liquidsamples are known. For example, pneumatic nebulisers, ultrasonicnebulisers, and thermospray nebulisers have been coupled to ICP-MSinstruments. A nebuliser converts a liquid sample into a spray, oraerosol, which is directed to a plasma/excitation device, either forionisation for mass spectrometry analysis downstream of the device, orfor excitation for optical emission/absorption analysis in the device.

FIG. 1 shows schematically conventional ICP-MS source. A liquid isintroduced into a spray chamber 10 using a nebuliser 12, which istypically driven by a flow of the same gas as the plasma gas (usuallyargon but sometimes helium). The spray chamber 10 may optionallyincorporate a line-of-sight obstruction (not shown), to prevent directdelivery of droplets into a sample tube, or injector, 14. It may alsooptionally incorporate a drain (not shown) for removal of excess liquidand a cooling device (not shown). The sample tube 14 is disposed withinan auxiliary gas tube 16, which is itself disposed inside a plasma torch18. Such a torch is shown in U.S. Pat. No. 7,273,996. Surrounding thetorch 18 is an induction coil 20 which is energised with an RF electriccurrent, typically at 27 or 40 MHz. A plasma gas—typically argon—issupplied via a plasma gas inlet 22 into the torch 18 and is convertedinto a plasma at a plasma region 24 towards the end of the torch. Theaerosol enters the torch 18 via the sample tube 14 and auxiliary gastube 16 and, due to the high temperature of the plasma, is ionised atthe plasma region 24. To help to introduce the nebulised sample into thecentre of the plasma region, an auxiliary gas flow is provided via anauxiliary gas inlet 26 into the auxiliary gas tube 16, so that both theplasma gas and the auxiliary gas surround the sample streamconcentrically. Finally, the sample ions are extracted from the plasmathrough a sampling aperture 28, to a mass analysing apparatus.

In ICP-OES, a similar configuration is used, except that the samplingaperture 28 is not required, since extraction to a mass spectrometerdoes not take place. Instead, optical emissions from the sample in theplasma region 24 are analysed with an optical spectrometer. Observationswith the spectrometer may be made from the back or from the side of theplasma region.

It is known that the efficiency of sample ionisation or of sampleexcitation for emission/absorption is affected by the size anddistribution in size of the sample droplets resulting from nebulisation.Large droplets and a wide distribution in droplet size lead to excessiveliquid injection into the torch and consequentially instability of theplasma due to the varying load. Contamination of the sample and skimmercones may also increase. Furthermore, because of the increased energyrequirement for evaporating larger droplets, incomplete atomisation andionisation of the sample may occur, resulting in molecularinterferences.

A general approach for improving the stability of the plasma is toincrease the size and power of the plasma generator, to cope with largesample droplets and variations in the droplet size. Another approachinvolves cooling the nebulisation spray chamber, to provide condenseddroplets on its walls. This leads to a shift of the liquid/gaseousequilibrium in the spray chamber, resulting in smaller droplets, by theremoval (evaporation) of solvent from the droplets to bring the partialpressure of the solvent back towards its required vapour pressure in thespray chamber as solvent condenses and is drained away.

A further approach involves providing a small diameter for the nebuliserneedle bore, with the aim of providing smaller droplets into the spraychamber. However, since ICP samples frequently have a high salt contentand comprise a certain proportion of unsolvated solid, precipitation ofsalts in the needle can result, eventually leading to blockage of thebore. Consequently, the bore diameter cannot be made very small and anadditional, desolvation or dehumidification step may be introduced totry to reduce the nebulised droplet size.

The above techniques for nebulisation and desolvation involve costlyspray chambers and spray chamber cooling, as well as the provision of anargon flow which may exceed what is actually needed for clean driving ofthe plasma itself. Despite the various developments discussed above,there is considerable room for improvement in the droplet formationtechnique.

There is a need therefore for an improved or alternative sampleexcitation apparatus and method for supplying and exciting a sample in aplasma generator, a flame, or another sample excitation device forsubsequent elemental analysis thereof. In particular, it would bedesirable to provide a sample excitation apparatus which comprises astandard ICP ionisation source. This invention aims to provide such anapparatus and method.

SUMMARY OF THE INVENTION

According to a first aspect of the invention, there is provided a sampleexcitation apparatus for a spectrometric analyser, the apparatuscomprising: a sample introduction stage comprising an electrospraynebuliser for generating a nebulised sample; and a sample excitationstage arranged to operate in an atmospheric pressure environment and toreceive and excite the nebulised sample in a sample excitation regionfor spectrometric analysis thereof.

The term “excitation” covers, for example, ionisation in ICP and MIP,flame excitation in AES, and optical excitation in AAS, among others.

Preferably, the electrospray nebuliser is arranged to discharge thenebulised sample directly into the sample excitation region.Alternatively, the sample introduction stage may comprise a spraychamber and the electrospray nebuliser may be arranged to discharge thenebulised sample into the spray chamber. Alternatively still, the sampleintroduction stage may comprise an auxiliary gas tube and theelectrospray nebuliser may be arranged to discharge the nebulised sampleinto the auxiliary gas tube.

Either way, it is preferable for a counter electrode to be configured aspart of, or at, the sample excitation region, the spray chamber, or theauxiliary gas tube. Preferably, a voltage source is arranged to effect apotential difference between the electrospray nebuliser and the counterelectrode. A controller may be arranged to control the voltage source toeffect a DC potential difference, a potential difference ofsubstantially fixed magnitude but alternating polarity, an alternatingpotential difference, or a combination of these.

In use, the nebulised sample is supplied from the electrospray nebuliserat an electrospray current, and the controller may in some embodimentsbe arranged to maintain the electrospray current at a substantiallyconstant value.

Preferably, a first gas supply of a first gas of relatively highelectron affinity, such as nitrogen, is arranged to be supplied at oraround the electrospray nebuliser and a second gas supply of a secondgas of relatively low electron affinity, such as argon, is arranged tobe supplied to the nebulised sample upstream of the sample excitationregion.

Preferably, a scavenging gas supply of an electron-scavenging gas, suchas one or more of sulphur hexafluoride, oxygen and benzene, is arrangedto be supplied to the sample introduction stage.

To help reduce or prevent surface charging effects, a nebulised sampledischarging means, for neutralising the nebulised sample downstream ofthe electrospray nebuliser may be provided.

Preferably, the sample excitation stage comprises a plasma generatorarranged to generate a plasma at the sample excitation region. This maybe an ICP—preferably a(n industry) standard ICP—a MIP, or a glowdischarge plasma generator. Alternatively, the sample excitation stagemay comprise a flame excitation source for optical spectrometricanalysis of the sample, such as for AAS or AES.

For some embodiments using chromatography or electrophoresis, theapparatus may further comprise a chromatographic or electrophoreticdevice arranged to supply the sample to the electrospray nebuliser.

According to a second aspect of the invention, there is provided amethod of exciting a sample for spectrometric analysis, comprisinggenerating a nebulised sample from an electrospray nebuliser; andreceiving and exciting the nebulised sample at a sample excitationregion operated in an atmospheric pressure environment.

According to a further aspect of the invention, there is provided theuse of an electrospray nebuliser in combination with an ionisation orexcitation source operated in an atmospheric pressure environment.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention may be put into practice in a number of ways and someembodiments will now be described, by way of non-limiting example, withreference to the following figures, in which:

FIG. 1 shows schematically a sectional view of a conventional ICPsource;

FIG. 2 shows schematically a sectional view of an embodiment with directelectrospray injection into a plasma;

FIG. 3 shows schematically a sectional view of an embodiment withelectrospray injection into a spray chamber;

FIG. 4 shows schematically a sectional view of an embodiment withelectrospray injection into an auxiliary gas tube;

FIG. 5 shows schematically a sectional view of an embodiment withelectrospray injection into an auxiliary gas tube having a grid helperelectrode; and

FIG. 6 shows schematically a sectional view of an embodiment employing aglow discharge plasma.

DESCRIPTION OF PREFERRED EMBODIMENTS

Although the invention finds application more widely, the use ofelectrospray nebulisation with plasma ionisation in an atmosphericpressure environment, especially ICP, will now be discussed. Generally,an analyte solution is fed through a nebuliser capillary, or needle,having an outlet end. At least some of the solution discharged from theoutlet end is fed to a plasma source. A potential difference is appliedbetween the needle, its outlet end or the analyte solution itself and aneffective electrode, which could be a tube, a grid or the plasma itselfto promote the formation of smaller droplets. The pressure of the plasmasource is similar to the pressure in the region just outside the needleoutlet end; namely, there is less than a ten-fold pressure differentialtherebetween. For example, the electrospray nebuliser may operate ataround 1 atm, while the plasma source operates at around 0.5 atm.Essentially, the plasma source operates in an atmospheric pressureenvironment.

FIG. 2 shows an arrangement in which an electrospray-nebulised sample isinjected directly into a plasma. An electrospray needle 30 is heldwithin an insulating injector 32 and is positioned a desired distancefrom a plasma region 34. A flow of a plasma gas 36, typically argon,surrounds the needle 30 concentrically, as a sheath gas, to keep thenebulised sample 38 in the hot, central part of the plasma region. Avoltage differential is generated between the needle 30 and the plasmaregion 34 and this is typically of the order of +0.5 kV to +10 kV. Forexample, in many ICP-MS sources, the plasma is held substantially atground potential, using source configurations known in the art. In thiscase, only a potential is applied to the needle 30 to enableelectrospraying of small droplets directly into the plasma. Thisarrangement will work best if the desolvation capabilities of the plasma(through its heat and the gas flow through it) are sufficient to copewith the liquid sample load.

The potential difference to be applied depends on the flow rate of thesample in the electrospray nebuliser. Generally, the flow rate can be inthe range from nanolitres per minute (nanospray), requiring only a fewhundred volts of potential for a spray with small droplets of uniformsize and a low variation of droplet size and composition over time, toseveral millilitres per minute, typically requiring a potentialdifference of several kilovolts for a typical spray distance of theorder of lcm. That is, the required electric field is in the region upto 10 kV/cm.

By providing a strong electric field, an excess of charge is created atthe end of the electrospray needle 30 containing the sample. Thepositive potential causes charge separation in the sample solution:anions travel towards the needle wall, while cations travel towards themeniscus of the droplet formed at the tip of the needle, forming a cone(the “Taylor cone”). When the electrostatic repulsion of the cations inthe cone overcomes the surface tension of the solution, charged dropletsare released from the tip. The positively charged droplets generallyfollow the electric field lines at the atmospheric pressure towards thecounter electrode (in FIG. 2, the plasma itself), but can be affected byspace charge and gas flow.

The Taylor cone effectively provides a reduced needle bore diameter, asthe droplets are not formed immediately from the bore, but from the tipof the cone. This results in the generation of smaller sample droplets,which accordingly present a lower plasma load on the plasma generator,allowing for more stable operation.

Depending on operational requirements, a number of features may bevaried to provide alternative configurations. For example, for highsample flow rates, a high-power atmospheric plasma, especially an ICP ispreferred. This is because it is able to offer the most stableperformance, even when the liquid flow or its ion content changes. Giventhe large region of the plasma at high temperature, the risk of theplasma being extinguished by, for example, the temporary admission ofmatter with greater heat capacity is reduced.

Conversely, for lower flow rates and variability of the analytesolution, the energy requirements for the plasma—that is, its power,density and size—are reduced. Accordingly, down to the limit of cloggingthe needle or the limit given by the desired dynamic range, a lowersample flow rate allows for a reduction in the size, power and pressureof the plasma. This, in turn, allows for a reduction in pressure for theoverall electrospray and plasma region: the pressure could be 10⁴ Pa,10³ Pa, down to several Pascals, or even lower, depending on the flowrate. A lower pressure or a smaller plasma size also affords a reductionin the flow rate of plasma gas (usually argon; occasionally helium)required to maintain a clean plasma and in the level of cooling requiredto prevent damage to components by the heat of the plasma.

The reduced-pressure alternative follows automatically when the sampleliquid flow rate is reduced, as a result of improved nebulisation byelectrospraying the sample from the needle. To avoid large pressuredifferentials between the sample introduction stage and the sampleionisation/excitation stage, the following features may be implementedin the plasma region. One clear feature is to seal the plasma regionagainst the surrounding atmosphere. A vacuum pump may also pump throughthe opening of a sampler cone and/or a vacuum pump may (directly) pumpthe plasma region. The flow rates of the plasma and cooling gases may bereduced and also the liquid flow rate may be reduced. The lower theliquid flow rate, the less heat is required to convert the liquid toatomic ions. This, in turn, allows the plasma to operate with a reducedsize and reduced power. Once the size and power of the plasma source arereduced, it is possible to reduce the plasma gas flow and the operatingpressure. Reducing the pressure of the plasma region may also makeextraction of the sample ions easier.

In some embodiments, it is not desirable for the plasma itself to formthe counter electrode for the electrospray. In such a case, anadditional electrode, for example a heat-resistant metal grid can beused. The grid could be made from tungsten, rhenium or rhodium, amongothers. With this arrangement, the spray characteristics can be madeindependent of the plasma conditions.

A further embodiment provides an arrangement in which a fluid splitteris disposed close to the electrospray needle tip. The sample liquid maythereby split between the plasma source and either a waste outlet or arecirculation device (so as not to use up too much sample). The purposeof this arrangement is to improve the liquid supply speed at low flowrates.

Starting from the direct injection shown in FIG. 2, the electrospraynebulisation can be provided anywhere upstream of the plasma. FIG. 3shows an embodiment which is generally similar to the arrangement ofFIG. 1, but with the conventional nebuliser 12 replaced by anelectrically assisted nebuliser needle 40. The needle is located in anspray chamber 42, though which an argon sheath gas 44 is also arrangedto flow. A counter electrode 46 draws the charged sample droplets 48into an injector 50, which discharges them into a plasma region 52, forionisation.

Generally, electro sprayed droplets are smaller and the droplet sizevariation has a lower standard deviation than droplets from conventionalnebulisers. This is particularly advantageous when the spray is nototherwise sufficiently stable. The naturally improved droplet size anddistribution reduce the need for additional separation of the droplets,as is known from the art; for example, in cooled cyclonic spray chamberswhere only small droplets are transmitted and bigger droplets are forcedto cold walls from where they are drained. Of course, cyclonic spraychambers can still be used to further improve the droplet sizedistribution.

In the embodiment of FIG. 3, a standard ICP ionisation source, arrangedfor operation in an atmospheric pressure environment, has been modifiedwith a new nebuliser arrangement: an electrically energised nebuliserneedle 40 for generating charged droplets and a counter electrode 46 forextracting the charged droplets into the injector 50 for supply to theplasma region 52.

The use of electrospray nebulisation in itself is already known. Inparticular, the technique is used in the mass spectrometric analysis oflarge, organic (molecular) samples, in electrospray ionisation massspectrometry (ESI-MS). Here, charged droplets are released from theTaylor cone, at the end of the electrospray needle, into an electrospraychamber. The eventual molecular ions are formed by desolvation of thepositively charged droplets in the electrospray chamber, to remove thesolvent from the droplets so that they increasingly shrink in size. Whenthe charged droplets are sufficiently small, charge repulsion becomesimportant and Coulombic fission takes place, breaking the droplets upand reducing their size still further. These processes continue untilmolecular ions are left.

In addition to the requirement for a spray chamber in ESI-MS, a cleandesolvation gas stream through the spray chamber is also required, as isa desolvation capillary or flow tube, which is usually heated, fortransferring molecular ions to the downstream mass spectrometer. The twohardware elements—the spray chamber and especially the heatedcapillary—are costly and the desolvation gas stream contributes to anelevated cost per analysis.

One ESI-MS arrangement, disclosed in U.S. Pat. No. 7,005,635, has theabove components, but the desolvation capillary has been modified with areduced pressure region relative to the sample introduction chamber. Arelatively small, low-power microwave-induced plasma (MIP) source isadded to the arrangement, at the reduced pressure region, as apost-processing stage after the electrospray ionisation of the sample.The “significant pressure differential” between the sample introductionchamber and the plasma region is essential for allowing this MIP sourceto be added to the ESI-MS. It is also stated that current ICP sourcescannot be integrated in an ESI-MS to provide the above post-processing.In any case, since (electrospray) ionisation takes place before the MIPsource, the above approach requires a desolvation spray chamber with adesolvation gas flow, the heated capillary known from ESI—but in amodified form for the reduced pressure region—and the plasma supportgas. It is thus relatively costly.

In significant contrast, the present invention provides sampleionisation or other sample excitation at an ionisation/excitation stagedownstream of the sample introduction stage comprising the electrosprayneedle, with the ionisation/excitation stage operating in an atmosphericpressure environment (e.g., at or near atmospheric pressure).Electrospray ionisation is not the starting point for the invention, norits objective, so the considerations for normal ESI do not need to betaken into account. This includes, in particular, the use of adesolvation capillary, which is not required: in an ICP sourceespecially, the ability to decompose molecules completely to elementalform means that small clusters in droplets with solvent will be easilyevaporated and atomised.

As previously discussed, unstable sample nebulisation directly affectsthe measurement accuracy and in serious cases leads to destabilisationof the plasma itself. With the use of an electrically energisednebuliser needle arrangement, the reduction in droplet size and dropletsize variation can be sufficient to gain ICP sensitivity and stabilitybetter than with standard nebulisers. Thus the overall detection limitof the instrument can be improved, or the measurement time reduced.

FIG. 4 shows an arrangement intermediate between the arrangement of FIG.3, with injection into the spray chamber, and the arrangement of FIG. 2,with direct injection into the plasma region. In the arrangement of FIG.4, the electrically nebulised sample is injected into an auxiliary gastube, which is used as the counter electrode for the electrospray. Theelectrospray needle 60 is housed in an injector 62, which itself ishoused in the auxiliary gas tube 64. Since the auxiliary gas tube 64serves as the counter electrode, an insulator 66 is disposed within thetube and surrounding the electrospray needle 60. The insulator has adownstream opening 68, to allow the nebulised sample 70 to pass to theplasma region 72. In this way, the electrospray needle 60 is shieldedfrom the electric field from the auxiliary gas tube 64 apart from at theinsulator opening 68, which thereby acts to extract the charged dropletsto the plasma. The auxiliary gas tube is made of a conductive metal,preferably platinum. Other metals alternatively be used, or ametal-coated or otherwise conductive auxiliary gas tube may be employed.Its potential is maintained at between −0.5 kV to −10 kV with respect tothe electrospray needle 60, depending on the sample flow rate. Argonplasma carrier gas 74,75 serves to direct the sample into the centre ofthe plasma.

FIG. 5 shows a similar, but alternative arrangement, in which thecounter electrode alternatively (although, in another embodiment, it mayadditionally) comprises a grid helper electrode 80, disposed at theoutlet end of the auxiliary gas tube 64. The helper electrode could be ametal plate or a shielding electrode, such as a tungsten or tantalumgrid.

The above configurations save on complex spray chambers, possibly alsoinjectors, and there is no need for heated desolvation capillaries,since the plasma and high-temperature region around it providesufficient heat for desolvation to occur anyway.

The above embodiments have the electrospray needle and theplasma/carrier gas flows parallel (generally concentric). However, it isdesirable in some embodiments to configure the electrospray needle andthe gas flow direction to the plasma region at certain angles withrespect to each other; for example, 20°, 45°, 66° or 90°. This can beespecially beneficial if it is desired to discard that part of thenebulised sample comprising the largest droplets, or if it is desired toselect from the nebulised sample distribution preformed molecular ions.

It will be understood that, depending on the application and flow rate,different spray distances (from the nebuliser needle to the plasmaregion, for example) may be advantageous. For lower flow rates, thedistances should generally be relatively small, starting from directinjection into the plasma and up to and beyond 1 cm distance; whereas,for higher flow rates, the distances should generally be longer.

The gas used in ICP sources is typically argon and it is convenient touse argon for injection and to assist in the nebulisation of the sample.The carrier gas can be directed in parallel flow with the injector, as asheath gas. Alternatively, the carrier gas may be in counterflow andpossibly pre-heated if it is desirable to provide additionaldesolvation. Reducing the sample droplet size in this region enables thesize and power of the plasma source to be reduced. Alternatively still,the carrier gas may be directed at an arbitrary angle; for example, atan angle relative to both the electrospray needle and the injector. Thiscan help to remove undesired portions of the sample spray, based on thecharge and droplet size.

It will be appreciated that a balance may be found between the operatingcosts associated with external desolvation—additional heat sources anddesolvating gas streams—and the operating costs associated with enablingthe plasma to cope with a high sample load, including increasing thepower consumption of the plasma source and increasing the amount ofplasma gas used. This balance will vary depending on the particularapplication at hand.

As to the electrical energising of the nebuliser needle, depending onthe flow rate of the sample, the spray voltage may range from around500V to around 10 kV (e.g. 500V, 1 kV, 2 kV, 3 kV, 5 kV, and 10 kV). Thevoltage applied may be positive or negative. Appropriate selection ofthe polarity can promote the detection of specific components in asample. The potential applied may be a fixed DC value, a value ofsubstantially fixed magnitude but alternating polarity, a time-varyingDC value, an AC voltage, or a combination of the above. More detail onthis is provided below.

The electrical energising of the nebuliser needle and/or itsco-operating counter electrode may be provided by a voltage sourcearranged to effect a potential difference therebetween. The voltagesource may be provided by a signal generator (possibly connected with asignal amplifier) in combination with a high-voltage output transformer.The signal generator may be selected depending on the type of waveform,if any, desired. For example, a function generator (for producing simplerepetitive waveforms, such as sine wave, sawtooth, step (pulse), square,and triangular waveforms) or an arbitrary waveform generator (forproducing arbitrary, user-defined waveforms) may be used. A controllercan be arranged to control the voltage source, to effect the desired DCor varying potential difference and/or to make real-time adjustments tothe voltage source, in order, for example, to maintain the electrospraycurrent of the nebulised sample at a substantially constant value.

One problem which has been recognised by the inventors whenincorporating an electrospray nebuliser in an ICP source arrangement ispronounced arcing. This is caused by the fact that the plasmagas—usually argon—is selected precisely for the property of good plasmaformation; that is, neutral argon has a low electron affinity, so isreadily ionised. In contrast, conventional techniques using electrospraynebulisation typically take place in an air or nitrogen environment.Nitrogen has a relatively high electron capture cross section resultingin a significantly higher position on the Paschen curve (the plot ofbreakdown voltage in a particular gas against the pressure of that gas)relative to argon. Accordingly, the arcing problem does notsignificantly affect electrospray ionisation arrangements.

Given the widespread use of ICP sources, especially in massspectrometry, many ICP operating parameters are subject to protocols andstandardisation. It is accordingly highly desirable to implement theelectrospray nebuliser sample introduction stage with a standard ICPsample excitation stage, rather than trying to introduce the industry toa new ICP operating regime. As such, the use of argon as the plasma gasshould preferably be left unchanged.

According to the Paschen curve, arcing, through electrical breakdown ofargon gas, becomes more likely when the pressure×length comes close tothe minimum of the Paschen curve. It is accordingly undesirable tooperate the system at a reduced pressure and operation in an atmosphericpressure environment is preferred. If desired, higher operatingpressures could be used, to move to a still more favourable position onthe Paschen curve (the alternative being use of extremely low voltages).

Another way of addressing the arcing, and consequential glow discharge,problem is by adjusting the inner and outer diameters of theelectrospray nebulisation needle. Increasing the diameters reduces thesharpness of the needle tip, thereby reducing the occurrence ofelectrical breakdown in the vicinity of the tip. For example, anelectrospray nebuliser needle, at 34 gauge (outer diameter: 0.18 mm;inner diameter: 0.1 mm), may be replaced by a needle at 32 gauge (outerdiameter: 0.23 mm; inner diameter: 0.15 mm). With such a change, it maybe desirable to supply the sample in a more diluted form, in order tokeep the rate of supply of the analyte molecules/atoms the same at theincreased liquid flow rate resulting from the change in diameter. It mayalso be desirable to reduce the surface tension of the liquid sample, bymixing it with tensid (e.g., Triton X-100).

An alternative approach is to use nitrogen as the carrier gas at theelectrospray nebulisation stage and to introduce the argon subsequently;for example, in an auxiliary gas tube, upstream of the plasma source.

A further alternative way of addressing the above problem is to mix inwith the argon carrier gas an electron scavenger, to reduce theconductive pathways for the arc/discharge. Suitable electron scavengersare sulphur hexafluoride (SF₆), benzene, oxygen, and benzene plusoxygen. Preferably, the electron scavenger employed will be readilydecomposed in the downstream plasma.

As mentioned above, the voltage applied to the electrospray nebulisationneedle may be alternated. This can help to avoid clogging of the needleand charge bias in the sample analysis. The frequency of alternation ofthe voltage could range from a few Hz to several kHz. Lower frequencyalternation will generally help to avoid the clogging of the needle byion separation and higher frequencies of alternation are advantageous inreducing a possible bias towards preformed positive or negative ionswithin polar solutions. It is understood that the droplet formationprocess for alternating current electrospray nebulisation appears to bedifferent from DC nebulisation and does not necessarily involve awell-formed Taylor cone.

The use of alternating spray voltages also has an impact on the abovearcing problem. Use of an alternating voltage can lead to a higherelectric breakdown voltage in argon. Also, the different nebulisationmechanism with AC nebulisation, compared with DC nebulisation, providesa lower spray onset voltage, which is dependent on the frequency of theAC voltage. That is, lower peak voltages may be employed, reducing thelikelihood of the argon breakdown voltage being reached.

Not all of the charged droplets sprayed from the electrically energisednebuliser needle are transferred to the excitation region (plasma, flameor other device), but instead come into contact with apparatuscomponents between the electrospray needle and the excitation region.This can cause surface charging on those apparatus components, which caninterfere with the nebulisation and/or subsequent passage to theexcitation region of the sample. In order to reduce or prevent thischarge-up, the nebulised sample droplets can be discharged downstream ofthe nebuliser needle. This can be achieved with an appropriatelyconfigured discharge grid or discharge needle.

The flow rate and composition of the carrier gas depend on the selectionof the plasma source. For ICP sources, the gas used is typically argon;for MIP sources, the gas used is either helium or hydrogen. An ignitionhelper gas, such as oxygen, may be added, if desired. Also, if a smallerICP source is desired, a counterflow argon carrier gas may be provided.

The sample liquid flow rate may lie in the range 1,3,5,100,200,500μl/min. The direct plasma injection arrangement has the potential ofreducing the sample flow rate to a few nanolitres per minute. To improvethe nebulisation of the sample further, instead of a normal solvent likea 2% aqueous solution of HNO₃, a purpose-made ionic liquid, such asethylammonium nitrate or 1-butyl-3-methylimidazolium salts, could beused.

The invention may be applied to analysers and plasmas of all types, asmentioned above. The most straightforward implementation is for ICP-MSand ICP-OES, since these already make use of nebuliser, spray chamber,injector and torch arrangements. As such, little structural modificationis required to implement the electrically assisted nebulisationtechnique.

Although plasma ionisation sources have been principally discussedabove, the invention may also be applied to atomic emission spectroscopyand atomic absorption spectroscopy. AES uses flame excitation, insteadof a plasma, to decompose molecules and stimulate atomic emissions,using the heat of the flame. The analyte emissions are detected using anoptical spectrometer. In AAS, a cooler flame is used, so that the sampleis desolvated and atomised, but the atoms are not excited out of theirground states. Light at various wavelengths is shone into the analysisregion, simultaneously or sequentially, and the amount of light absorbedat a particular wavelength determines the amount of a particular analytein the sample. In both cases, the use of electrically assistednebulisation of the sample facilitates the desolvation and atomisationof the sample before optical analysis takes place.

The invention may also be applied to other ionisation techniques; forexample, FIG. 6 shows an arrangement in which the ionisation source is aglow discharge plasma. US-A1-2007/0040112 describes a known glowdischarge source.

The plasma source comprises an annular anode 82, disposed on top of anannular cathode 84 and separated by insulators 86,87 and insulatingPeltier (cooling) elements 88. Argon plasma gas is provided to a supplytube 90 and passes into a central, plasma region 92. An outlet tube 94is in communication with the plasma region 92 for exhausting gastherefrom.

At the lower end of the plasma region 92, an electrospray nebulisationneedle 96 is provided, for supplying a nebulised sample into the plasmaregion. The argon gas is converted to a glow discharge plasma in theplasma region 92 and this plasma causes atomisation and ionisation ofthe nebulised sample as it is injected into the plasma region from thenebuliser needle 96. The (positive) sample ions are subsequently ejectedfrom the glow discharge plasma source, by the action of the anode 82,towards a downstream mass spectrometer or other spectrometric analyser.

If desired, the nebuliser needle 96 could directly form part of thecathode of the glow discharge arrangement, with the annular cathode 84.Alternatively, the nebuliser needle 96 could be the sole cathode of thearrangement. If it is not desired to make the nebuliser needle 96 partof the electrode arrangement for the glow discharge plasma source, thesprayed droplets could be fed into the needle 96 to be introduced intothe glow discharge source as a gas flow. This arrangement would work forboth a DC and an RF glow discharge.

In some embodiments, it may be desirable to include a sacrificialelectrode in the arrangement. Such an electrode, for example made fromcarbon, could be disposed around the outlet end of the nebuliser needle96, as indicated in FIG. 6 under reference numeral 98.

Another glow discharge plasma source which may be used as a sampleionisation device in one embodiment of the invention is described inRU2211502.

In the above embodiments, various sample analyses can be performed.These include the analysis of trace metals, isotope ratios, toxicelements and traces; and analyses in the environmental (e.g., water,soil), semiconductor, biomedical (e.g., blood-plasma, urine),petrochemical, food, nuclear (e.g., isotopes), and geochemical fields.The electrospray nebuliser may also be coupled to upstreamchromatographic devices, for use in liquid chromatography, HPLC andUHPLC ((ultra) high-performance liquid chromatography), ion exchangechromatography and electrophoresis. The separated analyte(s) can then befed to the electrospray nebuliser, for subsequent analysis.

Embodiments of the invention provide the possibility of reducing thetotal cost of ownership of, for example, an ICP-MS, by reducing theamount of argon used and by reducing the plasma size, thereby decreasingthe power requirement of the plasma source. Generally, embodiments ofthe invention provide a simplified and less expensive sampleintroduction assembly. By providing improved nebulisation of a sample,it is possible to improve the stability of the plasma and thereby toimprove measurement sensitivity. Since the nebulised droplet size isreduced, the total volume of sample used per analysis may be reduced.Since it is not necessary to provide a special nebuliser tip to theneedle—a straight tube ending for the nebuliser needle beingacceptable—a lower minimum flow rate (to prevent clogging of the needle)can be achieved. This is especially so in combination with variation ofthe voltage applied to the nebuliser needle, to prevent electrochemicalclogging.

1. An inductively coupled plasma sample ionisation apparatus for aspectrometric analyser, the apparatus comprising: a sample introductionstage comprising an electrospray nebuliser for generating a nebulisedsample; and a sample ionisation stage comprising an inductively coupledplasma generator arranged to operate in an atmospheric pressureenvironment and to generate an inductively coupled plasma at a sampleionisation region, the sample ionisation region being arranged toreceive and ionise the nebulised sample for spectrometric analysisthereof.
 2. The apparatus of claim 1, wherein the electrospray nebuliseris arranged to discharge the nebulised sample directly into the sampleionisation region.
 3. The apparatus of claim 2, wherein the sampleionisation region is configured with a potential difference relative tothe electrospray nebuliser, so as to serve as a counter electrode. 4.The apparatus of claim 1, wherein the sample introduction stage furthercomprises a spray chamber and the electrospray nebuliser is arranged todischarge the nebulised sample into the spray chamber.
 5. The apparatusof claim 4, wherein the spray chamber comprises a counter electrodedisposed downstream of the electrospray nebuliser.
 6. The apparatus ofclaim 1, wherein the sample introduction stage further comprises anauxiliary gas tube and the electrospray nebuliser is arranged todischarge the nebulised sample into the auxiliary gas tube.
 7. Theapparatus of claim 6, wherein the auxiliary gas tube is configured as acounter electrode, or comprises a counter electrode disposed downstreamof the electrospray nebuliser.
 8. The apparatus of claim 1, furthercomprising: a voltage source arranged to effect a potential differencebetween the electrospray nebuliser and a/the counter electrode; and acontroller arranged to control the voltage source to effect a DCpotential difference.
 9. The apparatus of claim 8, wherein, in use, thenebulised sample is supplied from the electrospray nebuliser at anelectrospray current, and the controller is arranged to maintain theelectrospray current at a substantially constant value.
 10. Theapparatus of claim 1, further comprising: a voltage source arranged toeffect a potential difference between the electrospray nebuliser anda/the counter electrode; and a controller arranged to control thevoltage source to effect an alternating potential difference.
 11. Theapparatus of claim 1, further comprising a first gas supply of a firstgas of relatively high electron affinity arranged to be supplied at oraround the electrospray nebuliser and a second gas supply of a secondgas of relatively low electron affinity arranged to be supplied to thenebulised sample upstream of the sample ionisation region.
 12. Theapparatus of claim 11, wherein the first gas is nitrogen and the secondgas is argon.
 13. The apparatus of claim 1, further comprising ascavenging gas supply of an electron-scavenging gas arranged to besupplied to the sample introduction stage.
 14. The apparatus of claim13, wherein the electron-scavenging gas comprises one or more of sulphurhexafluoride, oxygen and benzene.
 15. The apparatus of claim 1, furthercomprising a nebulised sample discharging means, for neutralising thenebulised sample downstream of the electrospray nebuliser. 16.(canceled)
 17. The apparatus of claim 1, wherein the plasma generator isa standard ICP generator.
 18. (canceled)
 19. (canceled)
 20. Theapparatus of claim 1, further comprising a chromatographic orelectrophoretic device arranged to supply the sample to the electrospraynebuliser.
 21. A method of ionising a sample for spectrometric analysis,comprising: generating a nebulised sample from an electrospraynebuliser; and receiving and ionising the nebulised sample at aninductively coupled plasma sample ionisation region operated in anatmospheric pressure environment.
 22. The method of claim 21, whereinthe nebulised sample is discharged directly into the sample ionisationregion.
 23. The method of claim 21, wherein the nebulised sample isdischarged into a spray chamber.
 24. The method of claim 21, wherein thenebulised sample is discharged into an auxiliary gas tube.
 25. Themethod of claim 21, comprising effecting a DC potential differencebetween the electrospray nebuliser and a counter electrode.
 26. Themethod of claim 25, wherein the nebulised sample is supplied from theelectrospray nebuliser at a substantially constant electrospray current.27. The method of claim 21, comprising effecting an alternatingpotential difference between the electrospray nebuliser and a counterelectrode.
 28. The method of claim 21, further comprising supplying afirst gas of relatively high electron affinity at or around theelectrospray nebuliser and supplying a second gas of relatively lowelectron affinity to the nebulised sample upstream of the sampleionisation region.
 29. The method of claim 28, wherein the first gas isnitrogen and the second gas is argon.
 30. The method of claim 21,further comprising supplying an electron-scavenging gas during thegenerating step.
 31. The method of claim 30, wherein theelectron-scavenging gas comprises one or more of sulphur hexafluoride,oxygen and benzene.
 32. The method of claim 21, further comprisingdischarging the nebulised sample downstream of the electrospraynebuliser.
 33. (canceled)
 34. (canceled)
 35. (canceled)
 36. (canceled)37. (canceled)
 38. A sample flame excitation apparatus for aspectrometric analyser, the apparatus comprising: a sample introductionstage comprising an electrospray nebuliser for generating a nebulisedsample; and a sample excitation stage comprising a flame excitationsource arranged to operate in an atmospheric pressure environment and toreceive and excite the nebulised sample in a sample excitation regionfor optical spectrometric analysis thereof.
 39. The apparatus of claim38, wherein the electrospray nebuliser is arranged to discharge thenebulised sample directly into the sample excitation region.
 40. Theapparatus of claim 39, wherein the sample excitation region isconfigured with a potential difference relative to the electrospraynebuliser, so as to serve as a counter electrode.
 41. The apparatus ofclaim 38, wherein the sample introduction stage further comprises aspray chamber and the electrospray nebuliser is arranged to dischargethe nebulised sample into the spray chamber.
 42. The apparatus of claim41, wherein the spray chamber comprises a counter electrode disposeddownstream of the electrospray nebuliser.
 43. The apparatus of claim 38,wherein the sample introduction stage further comprises an auxiliary gastube and the electrospray nebuliser is arranged to discharge thenebulised sample into the auxiliary gas tube.
 44. The apparatus of claim43, wherein the auxiliary gas tube is configured as a counter electrode,or comprises a counter electrode disposed downstream of the electrospraynebuliser.
 45. The apparatus of claim 38, further comprising: a voltagesource arranged to effect a potential difference between theelectrospray nebuliser and a counter electrode; and a controllerarranged to control the voltage source to effect an AC or DC potentialdifference.
 46. The apparatus of claim 38, further comprising a firstgas supply of a first gas of relatively high electron affinity arrangedto be supplied at or around the electrospray nebuliser and a second gassupply of a second gas of relatively low electron affinity arranged tobe supplied to the nebulised sample upstream of the sample excitationregion.
 47. The apparatus of claim 38, further comprising a scavenginggas supply of an electron-scavenging gas arranged to be supplied to thesample introduction stage.
 48. The apparatus of claim 47, wherein theelectron-scavenging gas comprises one or more of sulphur hexafluoride,oxygen and benzene.
 49. The apparatus of claim 38, further comprising anebulised sample discharging means, for neutralising the nebulisedsample downstream of the electrospray nebuliser.
 50. The apparatus ofclaim 38, further comprising a chromatographic or electrophoretic devicearranged to supply the sample to the electrospray nebuliser.
 51. Amethod of flame-exciting a sample for optical spectrometric analysis,comprising: generating a nebulised sample from an electrospraynebuliser; and receiving and flame-exciting the nebulised sample at asample excitation region operated in an atmospheric pressureenvironment.